JPH04363377A - Releasable sheet - Google Patents
Releasable sheetInfo
- Publication number
- JPH04363377A JPH04363377A JP16644291A JP16644291A JPH04363377A JP H04363377 A JPH04363377 A JP H04363377A JP 16644291 A JP16644291 A JP 16644291A JP 16644291 A JP16644291 A JP 16644291A JP H04363377 A JPH04363377 A JP H04363377A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- adhesive
- silicone resin
- resin
- release sheet
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010410 layer Substances 0.000 claims abstract description 125
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 36
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 30
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 30
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012790 adhesive layer Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 8
- 239000011347 resin Substances 0.000 claims abstract description 8
- 229920002050 silicone resin Polymers 0.000 claims description 62
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 abstract description 42
- 230000001070 adhesive effect Effects 0.000 abstract description 42
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 28
- -1 polypropylene Polymers 0.000 abstract description 27
- 239000000758 substrate Substances 0.000 abstract description 17
- 229910052697 platinum Inorganic materials 0.000 abstract description 14
- 125000003342 alkenyl group Chemical group 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 6
- 229920001778 nylon Polymers 0.000 abstract description 6
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 4
- 239000004743 Polypropylene Substances 0.000 abstract description 3
- 229920001155 polypropylene Polymers 0.000 abstract description 3
- 239000004745 nonwoven fabric Substances 0.000 abstract description 2
- 238000006757 chemical reactions by type Methods 0.000 abstract 2
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 abstract 1
- 239000011342 resin composition Substances 0.000 description 26
- 238000004519 manufacturing process Methods 0.000 description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 18
- 238000001723 curing Methods 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000007259 addition reaction Methods 0.000 description 9
- 239000003960 organic solvent Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002759 woven fabric Substances 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 230000001588 bifunctional effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- 239000002985 plastic film Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- BITPLIXHRASDQB-UHFFFAOYSA-N ethenyl-[ethenyl(dimethyl)silyl]oxy-dimethylsilane Chemical compound C=C[Si](C)(C)O[Si](C)(C)C=C BITPLIXHRASDQB-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- JMYZLRSSLFFUQN-UHFFFAOYSA-N (2-chlorobenzoyl) 2-chlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC=C1C(=O)OOC(=O)C1=CC=CC=C1Cl JMYZLRSSLFFUQN-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BYPFICORERPGJY-UHFFFAOYSA-N 3,4-diisocyanatobicyclo[2.2.1]hept-2-ene Chemical compound C1CC2(N=C=O)C(N=C=O)=CC1C2 BYPFICORERPGJY-UHFFFAOYSA-N 0.000 description 1
- REEBWSYYNPPSKV-UHFFFAOYSA-N 3-[(4-formylphenoxy)methyl]thiophene-2-carbonitrile Chemical compound C1=CC(C=O)=CC=C1OCC1=C(C#N)SC=C1 REEBWSYYNPPSKV-UHFFFAOYSA-N 0.000 description 1
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- OZJPLYNZGCXSJM-UHFFFAOYSA-N delta-Valerolactone Natural products O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 125000005358 mercaptoalkyl group Chemical group 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 210000001685 thyroid gland Anatomy 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は新規な離形性シート、さ
らに詳しくは、離形性及びその耐久性に優れるとともに
簡単な工程で容易に製造しうる、粘着性物質を取り扱う
場合に用いられる離形性シートに関するものである。[Industrial Application Field] The present invention is a novel release sheet, more specifically, it has excellent release properties and durability, and can be easily manufactured in a simple process, and is used when handling adhesive substances. This relates to a release sheet.
【０００２】0002
【従来の技術】従来、粘着性物質を取り扱う場合には、
通常取り扱いを容易にするために離形性シートが利用さ
れており、そしてこの離形性シートとしては、一般に紙
やプラスチックフイルムなどの支持基体の少なくとも片
面に、離形性硬化シリコーン樹脂層を有するものが用い
られている。しかしながら、このような紙やプラスチッ
クフイルムなどの支持基体表面に直接離形性硬化シリコ
ーン樹脂層を設けたものは、繰り返し使用する場合、該
離形性硬化シリコーン樹脂層が支持基体から脱落して離
形機能が失われるなど、耐久性が不十分であり、繰り返
し使用回数が制限されるのを免れないという欠点を有し
ている。また、支持基体表面に、まず反応型シリコーン
樹脂硬化層を設け、さらにその上に反応型シリコーン樹
脂硬化層を形成させた防汚染性シートが開示されている
（特開昭５９−２９１５７号公報）。このものも離形性
シートとして使用しうるが、製造工程が煩雑であって、
製造コストが高くつくのを免れない。さらに、このよう
なシリコーン樹脂コーティングシートには、従来、シリ
コーン樹脂としてミラブル型シリコーンエラストマーが
一般的に使用されるが、このミルブル型シリコーンエラ
ストマーは、例えば白金系や過酸化物系触媒を用いて加
熱硬化させ、機械的強度をもたせる必要があり、この場
合、加熱硬化条件として、通常１６０〜２００℃の範囲
の温度において数時間程度保持される。したがって、長
尺なシート製品を工業的に連続生産する場合、製造工程
が煩雑となるのを免れないという問題が生じる（特開昭
５９−２９１５７号公報）。[Prior Art] Conventionally, when handling sticky substances,
A release sheet is usually used to facilitate handling, and the release sheet generally has a release cured silicone resin layer on at least one side of a supporting substrate such as paper or plastic film. something is being used. However, when a mold-release cured silicone resin layer is directly provided on the surface of a supporting substrate such as paper or plastic film, when used repeatedly, the mold-release cured silicone resin layer may fall off and separate from the supporting substrate. It has the disadvantage that its durability is insufficient, such as loss of form and function, and the number of times it can be used repeatedly is inevitably limited. Furthermore, an antifouling sheet has been disclosed in which a cured layer of a reactive silicone resin is first provided on the surface of a supporting substrate, and then a cured layer of a reactive silicone resin is further formed thereon (Japanese Unexamined Patent Publication No. 59-29157). . This material can also be used as a release sheet, but the manufacturing process is complicated and
It is inevitable that manufacturing costs will be high. Furthermore, in such silicone resin coated sheets, millable silicone elastomers are generally used as the silicone resin, but these millable silicone elastomers are heated using, for example, platinum-based or peroxide-based catalysts. It is necessary to harden the material to give it mechanical strength, and in this case, the heat curing condition is usually maintained at a temperature in the range of 160 to 200° C. for several hours. Therefore, when long sheet products are produced continuously on an industrial scale, a problem arises in that the manufacturing process inevitably becomes complicated (Japanese Unexamined Patent Publication No. 59-29157).
【０００３】0003
【発明が解決しようとする課題】本発明はこのような従
来の離形性シートが有する欠点を克服し、離形性及びそ
の耐久性に優れる上、長尺シート製品でも簡単な工程で
工業的に容易に連続生産しうる粘着性物質取り扱い支持
用離形性シートを提供することを目的としてなされたも
のである。[Problems to be Solved by the Invention] The present invention overcomes the drawbacks of conventional mold release sheets, has excellent mold releasability and durability, and can also be used for long sheet products in a simple process. The purpose of this invention is to provide a releasable sheet for handling and supporting adhesive substances that can be easily and continuously produced.
【０００４】0004
【課題を解決するための手段】本発明者らは前記の好ま
しい性質を有する離形性シートを開発すべく鋭意研究を
重ねた結果、支持基体の片面又は両面に複数の特定の層
を設けた積層シートにより、その目的を達成しうること
を見い出し、この知見に基づいて本発明を完成するに至
った。すなわち、本発明は、支持基体の片面又は両面に
、所望に応じて設けられる（Ａ）接着剤層、（Ｂ）粉末
状無水ケイ酸含有ウレタン系樹脂又はアクリル系樹脂層
及び（Ｃ）反応型シリコーン系樹脂硬化層を順次設けて
成る離形性シート、及び支持基体の片面に、所望に応じ
て設けられる（Ａ）接着剤層、（Ｂ）粉末状無水ケイ酸
含有ウレタン系樹脂又はアクリル系樹脂層及び（Ｃ）反
応型シリコーン系樹脂硬化層を順次設け、かつ該支持基
体の他方の面に、感圧接着剤層を、さらに場合により剥
離用シートを設けて成る離形性シートを提供するもので
ある。[Means for Solving the Problems] As a result of intensive research to develop a release sheet having the above-mentioned preferable properties, the present inventors have provided a plurality of specific layers on one or both sides of a supporting substrate. It was discovered that the object could be achieved by using a laminated sheet, and the present invention was completed based on this knowledge. That is, the present invention provides (A) an adhesive layer, (B) a powdered silicic anhydride-containing urethane resin or acrylic resin layer, and (C) a reactive type resin layer, which are provided on one or both sides of a supporting substrate as desired. (A) adhesive layer, (B) powdered silicic anhydride-containing urethane resin or acrylic resin, which is optionally provided on one side of a mold release sheet consisting of a silicone resin cured layer and a support base, as desired. Provided is a releasable sheet comprising a resin layer and (C) a cured reactive silicone resin layer sequentially provided, and a pressure sensitive adhesive layer and optionally a release sheet provided on the other surface of the support base. It is something to do.
【０００５】以下、本発明を詳細に説明する。本発明の
離形性シートにおいて用いられる支持基体については特
に制限はなく、従来離形性シートの支持基体として慣用
されているものの中から任意のものを選択して用いるこ
とができる。このような支持基体としては、例えばポリ
エチレン、ポリプロピレン、ポリエステル、ポリ塩化ビ
ニル、ポリ塩化ビニリデン、ポリスチレン、ポリアミド
、ポリカーボネートなどから成るプラスチックシート、
ナイロン繊維、芳香族ポリアミド繊維、ポリエステル繊
維、アクリル系繊維、ポリプロピレン繊維、木綿、レー
ヨンなどから成る繊布又は不繊布、さらには紙などが挙
げられる。[0005] The present invention will be explained in detail below. There are no particular limitations on the support substrate used in the release sheet of the present invention, and any support substrate can be selected from those conventionally used as support substrates for release sheets. Such supporting substrates include, for example, plastic sheets made of polyethylene, polypropylene, polyester, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, polycarbonate, etc.
Examples include woven or nonwoven fabrics made of nylon fibers, aromatic polyamide fibers, polyester fibers, acrylic fibers, polypropylene fibers, cotton, rayon, and the like, as well as paper.
【０００６】本発明の離形性シートは、前記支持基体の
片面又は両面に、所望に応じて設けられる（Ａ）層、（
Ｂ）層及び（Ｃ）層を順次形成させることにより得られ
る。支持基体上に所望に応じて設けられる（Ａ）層は、
支持基体と（Ｂ）層とを緊密に密着させるための接着剤
層であって、該支持基体と（Ｂ）層とが緊密な密着性を
有する組合せの場合には、支持基体上に、（Ａ）層を設
けずに直接（Ｂ）層を設けてもよい。例えばプラスチッ
クシートなどの表面が平滑な支持基体の場合には（Ａ）
層を設けなくてもよい。The releasable sheet of the present invention comprises a layer (A) provided on one or both sides of the supporting substrate as desired;
It is obtained by sequentially forming layer B) and layer (C). The (A) layer provided on the supporting base as desired is:
An adhesive layer for tightly adhering the support base and the (B) layer, in the case of a combination where the support base and the (B) layer have close adhesion, on the support base, ( The (B) layer may be directly provided without providing the A) layer. For example, in the case of a support substrate with a smooth surface such as a plastic sheet, (A)
It is not necessary to provide a layer.
【０００７】この（Ａ）層の形成に用いられる接着剤に
ついては、支持基体と（Ｂ）層とを緊密に密着させうる
ものであればよく、特に制限はないが、柔軟性を有する
ものが好ましく、例えばウレタン樹脂系接着剤やアクリ
ル樹脂系接着剤などが好ましく用いられる。なお、（Ｂ
）層にウレタン系樹脂を用いた場合には、該接着剤とし
てウレタン樹脂系接着剤を、アクリル系樹脂を用いた場
合にはアクリル樹脂系接着剤を用いるのが有利である。
この接着剤は溶剤型、エマルジョン型のいずれであって
もよい。The adhesive used to form layer (A) is not particularly limited as long as it can bring the supporting substrate and layer (B) into close contact, but adhesives that are flexible are preferred. Preferably, for example, a urethane resin adhesive or an acrylic resin adhesive is used. In addition, (B
) When a urethane resin is used for the layer, it is advantageous to use a urethane resin adhesive, and when an acrylic resin is used, an acrylic resin adhesive is advantageously used as the adhesive. This adhesive may be either a solvent type or an emulsion type.
【０００８】本発明の離形性シートにおける（Ｂ）層に
は、粉末状無水ケイ酸含有ウレタン系樹脂又はアクリル
系樹脂が用いられる。このウレタン系樹脂又はアクリル
系樹脂に含有させる粉末状無水ケイ酸は、該（Ｂ）層に
よって、（Ｃ）層の反応型シリコーン系樹脂の硬化反応
が阻害されるのを防止する作用を有するとともに、（Ｂ
）層と（Ｃ）層との接着力を向上させる作用を有してい
る。[0008] For the layer (B) in the mold release sheet of the present invention, a powdered silicic anhydride-containing urethane resin or acrylic resin is used. The powdered silicic anhydride contained in the urethane resin or acrylic resin has the effect of preventing the curing reaction of the reactive silicone resin of the layer (C) from being inhibited by the layer (B). , (B
) layer and layer (C).
【０００９】（Ｃ）層の反応型シリコーン系樹脂硬化層
の形成には、通常硬化速度が極めて速い白金触媒を用い
る付加反応型シリコーン系樹脂組成物が好ましく用いら
れ、この組成物にはオルガノハイドロジエンポリシロキ
サンが添加されるが、このものは、（Ｂ）層にウレタン
系樹脂を用いた場合、該ウレタン系樹脂中に存在する官
能基と作用しやすく、その結果硬化反応が阻害されると
いう好ましくない事態を招来する。該粉末状無水ケイ酸
を（Ｂ）層に含有させた場合、前記のような（Ｃ）層の
反応型シリコーン系樹脂の硬化反応が阻害されるのが防
止される。[0009] For the formation of the reactive silicone resin cured layer of layer (C), an addition reaction silicone resin composition using a platinum catalyst, which usually has an extremely fast curing rate, is preferably used. Diene polysiloxane is added, but when a urethane resin is used in the (B) layer, it tends to interact with the functional groups present in the urethane resin, and as a result, the curing reaction is inhibited. bring about an undesirable situation. When the powdered silicic anhydride is contained in the layer (B), the curing reaction of the reactive silicone resin in the layer (C) as described above is prevented from being inhibited.
【００１０】また、（Ｂ）層として粉末状無水ケイ酸を
含有しないウレタン系樹脂又はアクリル系樹脂から成る
層を用いた場合、このものと（Ｃ）層の反応型シリコー
ン系樹脂硬化層との接着強度が低く、特に（Ｃ）層を形
成させるための反応型シリコーン系樹脂組成物を調製し
てから硬化させるまでの時間が長くなるに伴い、該（Ｂ
）層と（Ｃ）層との接着強度の低下が著しくなる。
該粉末状無水ケイ酸を（Ｂ）層に含有させた場合、この
（Ｂ）層と（Ｃ）層間の接着力が著しく向上するととも
に、（Ｃ）層を形成させるための反応型シリコーン系樹
脂組成物を調製してから硬化させるまでの時間がある程
度長くなっても、（Ｂ）層と（Ｃ）層間の接着力が大き
く低下することがない。また、粉末状無水ケイ酸を（Ｃ
）層の反応型シリコーン系樹脂硬化層に含有させた場合
、前記のような接着力の改善効果は十分に発揮されず、
（Ｃ）層が補強される効果がみられるのみである。[0010] Furthermore, when a layer made of urethane resin or acrylic resin that does not contain powdered silicic acid anhydride is used as layer (B), the bond between this layer and the cured reactive silicone resin layer of layer (C) is Adhesive strength is low, especially as the time from preparation to curing of the reactive silicone resin composition for forming layer (C) becomes longer.
) The adhesive strength between the layer (C) and the layer (C) decreases significantly. When the powdered silicic anhydride is contained in the (B) layer, the adhesive strength between the (B) layer and the (C) layer is significantly improved, and the reactive silicone resin for forming the (C) layer is Even if the time from preparing the composition to curing it becomes long to some extent, the adhesive strength between the layer (B) and the layer (C) does not decrease significantly. In addition, powdered silicic anhydride (C
) When it is included in the reactive silicone resin cured layer of the layer, the above-mentioned adhesive strength improvement effect is not sufficiently exhibited,
(C) Only the effect of reinforcing the layer is observed.
【００１１】該粉末状無水ケイ酸としては、平均粒子径
が０．１〜５０μｍの範囲にあるものが好ましく用いら
れ、またその含有量は（Ｂ）層を構成するウレタン系樹
脂又はアクリル系樹脂１００重量部に対し、通常１〜５
０重量部の範囲で選ばれる。この量が１重量部未満では
粉末状無水ケイ酸を含有させた効果が十分に発揮されな
いし、５０重量部を超えるとその量の割には効果の向上
がみられず、むしろ（Ｂ）層の柔軟性が低下し、好まし
くない。[0011] As the powdered silicic anhydride, one having an average particle diameter in the range of 0.1 to 50 μm is preferably used, and the content thereof is determined by the urethane resin or acrylic resin constituting the layer (B). Usually 1 to 5 per 100 parts by weight
It is selected within the range of 0 parts by weight. If this amount is less than 1 part by weight, the effect of containing powdered silicic anhydride will not be fully exhibited, and if it exceeds 50 parts by weight, no improvement in the effect will be seen for the amount, but rather the (B) layer The flexibility of the material decreases, which is undesirable.
【００１２】この粉末状無水ケイ酸は所望により、シラ
ンカップリング剤などにより表面処理したものを用いる
ことができる。該粉末状無水ケイ酸としては、例えばカ
ーブレックス（塩野義製薬社製、商品名）、サイロイド
（富士デビソン社製、商品名）、エロアジール（日本エ
ロアジール社製、商品名）、エロアジール９７２（日本
エロアジール社製、シランカップリング剤処理品、商品
名）、ファインシール（徳山曹達社製、商品名）、レオ
シール（徳山曹達社製、商品名）、ニップシール（日本
リカ社製、商品名）、ミズカシール（水沢化学社製、商
品名）などが市販されている。[0012] If desired, this powdered silicic anhydride may be surface-treated with a silane coupling agent or the like. Examples of the powdered silicic anhydride include Carbrex (manufactured by Shionogi & Co., Ltd., trade name), Cyroid (manufactured by Fuji Davison Co., Ltd., trade name), EloAsil (manufactured by Nippon EloAgil Co., Ltd., trade name), and EloAgil 972. (manufactured by Nippon Eloasil Co., Ltd., product treated with silane coupling agent, product name), Fine Seal (manufactured by Tokuyama Soda Co., Ltd., product name), Reoseil (manufactured by Tokuyama Soda Co., Ltd., product name), Nip Seal (manufactured by Nippon Rica Co., Ltd., product name) ), Mizuka Seal (manufactured by Mizusawa Chemical Co., Ltd., trade name), etc. are commercially available.
【００１３】前記ウレタン系樹脂としては、通常分子量
７００〜６０００の２官能末端水酸基含有ポリオールと
ジイソシアネート化合物と必要に応じて用いられる鎖伸
長剤とを反応させて得られたものが用いられる。分子量
７００〜６０００の２官能末端水酸基含有ポリオールと
しては、例えばポリエチレングリコール、ポリオキシプ
ロピレングリコール、ポリテトラメチレングリコール、
エチレンオキシド／プロピレンオキシド共重合体などの
ポリエーテルポリオール；バレロラクトンポリオール、
ポリカプロラクトンポリオール、ポリカーボネートジオ
ール、さらにはアジピン酸、セバチン酸、アゼライン酸
、イソフタル酸、テレフタル酸、マレイン酸、フマル酸
、ダイマー酸などの二塩基酸とエチレングリコール、ジ
エチレングリコール、プロピレングリコール、ブタンジ
オール、ヘキサンジオール、ネオペンチルジオール、ダ
イマージオールなどのジオールとから得られるポリオー
ルなどのポリエステルポリオールなどが挙げられる。The urethane resin used is usually one obtained by reacting a bifunctional terminal hydroxyl group-containing polyol with a molecular weight of 700 to 6,000, a diisocyanate compound, and a chain extender used as necessary. Examples of polyols containing bifunctional terminal hydroxyl groups with a molecular weight of 700 to 6,000 include polyethylene glycol, polyoxypropylene glycol, polytetramethylene glycol,
Polyether polyols such as ethylene oxide/propylene oxide copolymers; valerolactone polyols,
Polycaprolactone polyols, polycarbonate diols, and dibasic acids such as adipic acid, sebacic acid, azelaic acid, isophthalic acid, terephthalic acid, maleic acid, fumaric acid, and dimer acid, as well as ethylene glycol, diethylene glycol, propylene glycol, butanediol, and hexane. Examples include polyester polyols such as polyols obtained from diols such as diols, neopentyl diols, and dimer diols.
【００１４】ジイソシアネート化合物としては、例えば
トリレンジイソシアネート、キシリレンジイソシアネー
ト、ジフェニルメタンジイソシアネート、ナフチレンジ
イソシアネートなどの芳香族ジイソシアネート化合物、
イソホロンジイソシアネート、水素添加キシリレンジイ
ソシアネート、水素添加ジフェニルメタンジイソシアネ
ート、ノルボルネンジイソシアネートなどの脂環式ジイ
ソシアネート化合物、ヘキサメチレンジイソシアネート
、ダイマージイソシアネートなどの脂肪族ジイソシアネ
ート化合物などが挙げられる。Examples of the diisocyanate compound include aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, and naphthylene diisocyanate;
Examples include alicyclic diisocyanate compounds such as isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and norbornene diisocyanate, and aliphatic diisocyanate compounds such as hexamethylene diisocyanate and dimer diisocyanate.
【００１５】また、鎖伸長剤としては、例えばエチレン
グリコール、ジエチレングリコール、プロピレングリコ
ール、ブタンジオール、ヘキサンジオールなどのジオー
ル化合物、イソホロンジアミン、ヘキサメチレンジアミ
ン、キシリレンジアミンなどの脂環式、脂肪族、芳香族
ジアミン化合物などが挙げられる。一方、アクリル系樹
脂としては、アクリル酸アルキルエステル単位を主構成
単位とする弾性体が用いられる。このようなものとして
は、例えばアクリル酸エチルやアクリル酸ブチルを主成
分とし、これにアクリロニトリルや、２−クロロエチル
ビニルエーテル、アクリル酸グリシジル、アリルグリシ
ジルエーテル、エチリデンノルボルネンのような架橋性
モノマーなどのコモノマーを加え、共重合させて成るも
のなどが挙げられる。Examples of chain extenders include diol compounds such as ethylene glycol, diethylene glycol, propylene glycol, butanediol, and hexanediol, and alicyclic, aliphatic, and aromatic compounds such as isophorone diamine, hexamethylene diamine, and xylylene diamine. Examples include group diamine compounds. On the other hand, as the acrylic resin, an elastic body whose main constituent unit is an acrylic acid alkyl ester unit is used. Examples of such materials include ethyl acrylate and butyl acrylate as main components, and comonomers such as acrylonitrile, 2-chloroethyl vinyl ether, glycidyl acrylate, allyl glycidyl ether, and crosslinking monomers such as ethylidene norbornene. Examples include those obtained by adding and copolymerizing.
【００１６】前記ウレタン系樹脂やアクリル系樹脂は有
機溶媒に溶解させた溶液型として用いてもよいし、エマ
ルジョン型として用いてもよく、また、本発明の目的が
損なわれない範囲で、他の樹脂と混合して用いてもよい
。該（Ｂ）層の厚さは通常１０〜１００μｍの範囲で選
ばれる。本発明の離形性シートにおいては、前記（Ｂ）
層の上に、（Ｃ）層として反応型シリコーン系樹脂硬化
層が設けられる。この（Ｃ）層は離形層であって、粘着
性物質の表面にこの（Ｃ）層が接するように本発明の離
形性シートを密着させた場合、該離形性シートは粘着性
物質から容易に剥離することができる。The urethane resin and acrylic resin may be used in the form of a solution dissolved in an organic solvent, or may be used in the form of an emulsion. It may be used in combination with a resin. The thickness of the layer (B) is usually selected within the range of 10 to 100 μm. In the release sheet of the present invention, the above (B)
A reactive silicone resin cured layer is provided on the layer as the (C) layer. This layer (C) is a release layer, and when the release sheet of the present invention is brought into close contact with the surface of an adhesive material so that the layer (C) is in contact with the surface of the adhesive material, the release sheet It can be easily peeled off.
【００１７】該（Ｃ）層を形成するには、反応型シリコ
ーン系樹脂組成物から成る層を前記（Ｂ）層上に設け硬
化させればよい。反応型シリコーン系樹脂組成物として
は、例えば付加反応型、紫外線硬化型、加熱硬化型など
のシリコーン系樹脂組成物が挙げられる。反応型シリコ
ーン系樹脂組成物としては、例えばアルケニル基含有オ
ルガノポリシロキサンとオルガノハイドロジエンポリシ
ロキサンと白金系触媒とを含有して成る組成物が挙げら
れる。該アルケニル基含有オルガノポリシロキサンとし
ては、例えば一般式To form the layer (C), a layer made of a reactive silicone resin composition may be provided on the layer (B) and cured. Examples of the reactive silicone resin composition include addition reaction type, ultraviolet curing type, and heat curing type silicone resin compositions. Examples of the reactive silicone resin composition include a composition containing an alkenyl group-containing organopolysiloxane, an organohydrodiene polysiloxane, and a platinum catalyst. As the alkenyl group-containing organopolysiloxane, for example, the general formula
【００１８】[0018]
【化１】[Chemical formula 1]
【００１９】で表される化合物などが好ましく用いられ
る。前記一般式［１］におけるＲ１及びＲ２は、それぞ
れアルケニル基、Ｘ１はメチル基であるが、Ｘ１の一部
はフェニル基又はアルケニル基で置換されていてもよく
、Ｘ１の一部がアルケニル基で置換されている場合には
、Ｒ１及びＲ２の少なくとも１つはメチル基又はフェニ
ル基で置換されていてもよい。Ｒ３及びＲ４はメチル基
又はフェニル基、ｎは１以上の整数である。該アルケニ
ル基としてはビニル基やアリル基などが挙げられるが、
これらの中で特にビニル基が好適である。Compounds represented by the following are preferably used. In the general formula [1], R1 and R2 are each an alkenyl group, and X1 is a methyl group, but a part of X1 may be substituted with a phenyl group or an alkenyl group, and a part of X1 is an alkenyl group. When substituted, at least one of R1 and R2 may be substituted with a methyl group or a phenyl group. R3 and R4 are a methyl group or a phenyl group, and n is an integer of 1 or more. Examples of the alkenyl group include a vinyl group and an allyl group,
Among these, vinyl groups are particularly preferred.
【００２０】このアルケニル基含有オルガノポリシロキ
サンとしては、メチルビニルシロキサン単位の含有量が
１．０〜２０モル％の範囲にあり、かつ平均重合度が１
０〜２００で、温度２５℃における粘度が２００〜２０
００ｃｐｓの範囲にあるものが好適である。一方、オル
ガノハイドロジエンポリシロキサンとしては、例えば一
般式The alkenyl group-containing organopolysiloxane has a content of methylvinylsiloxane units in the range of 1.0 to 20 mol% and an average degree of polymerization of 1.
0 to 200, and the viscosity at a temperature of 25°C is 200 to 20.
A value in the range of 00 cps is preferable. On the other hand, as organohydrodiene polysiloxane, for example, the general formula
【００２１】[0021]
【化２】[Case 2]
【００２２】で表される化合物などが好ましく用いられ
る。前記一般式［２］におけるＲ５及びＲ６は、それぞ
れ水素原子、Ｘ２はメチル基であるが、Ｘ２の一部はフ
ェニル基又は水素原子で置換されていてもよく、Ｘ２の
一部が水素原子で置換されている場合には、Ｒ５及びＲ
６の少なくとも１つはメチル基又はフェニル基で置換さ
れていてもよい。Ｒ７及びＲ８はそれぞれメチル基又は
フェニル基、ｍは１以上の整数である。Compounds represented by the following are preferably used. In the general formula [2], R5 and R6 are each a hydrogen atom and X2 is a methyl group, but a part of X2 may be substituted with a phenyl group or a hydrogen atom, and a part of X2 is a hydrogen atom. If substituted, R5 and R
At least one of 6 may be substituted with a methyl group or a phenyl group. R7 and R8 are each a methyl group or a phenyl group, and m is an integer of 1 or more.
【００２３】このオルガノハイドロジエンポリシロキサ
ンとしては、平均重合度が１０〜１００で、温度２５℃
における粘度が１０〜２００ｃｐｓの範囲にあるものが
好適である。また、白金系触媒としては、例えば白金と
テトラメチルジビニルジシロキサンとの錯体などが好ま
しく用いられる。該付加反応型シリコーン系樹脂組成物
は通常有機溶媒、好ましくは芳香族系溶媒中に、前記の
アルケニル基含有オルガノポリシロキサンとオルガノハ
イドロジエンポリシロキサンと白金系触媒とを溶解させ
て、溶液の形で用いられる。この際、アルケニル基含有
オルガノポリシロキサンとオルガノハイドロジエンポリ
シロキサンとの使用割合については、アルケニル基含有
オルガノポリシロキサン１００重量部に対し、オルガノ
ハイドロジエンポリシロキサンを５〜２０重量部の割合
で用いるのが望ましい。[0023] This organohydrodiene polysiloxane has an average degree of polymerization of 10 to 100 and a temperature of 25°C.
It is preferable that the viscosity is in the range of 10 to 200 cps. Further, as the platinum-based catalyst, for example, a complex of platinum and tetramethyldivinyldisiloxane is preferably used. The addition-reactive silicone resin composition is prepared by dissolving the alkenyl group-containing organopolysiloxane, organohydrodiene polysiloxane, and platinum catalyst in an organic solvent, preferably an aromatic solvent. used in At this time, regarding the ratio of the alkenyl group-containing organopolysiloxane and the organohydrodiene polysiloxane, the organohydrodiene polysiloxane is used in a ratio of 5 to 20 parts by weight per 100 parts by weight of the alkenyl group-containing organopolysiloxane. is desirable.
【００２４】また、この付加反応型シリコーン系樹脂組
成物には、所望に応じビニル基含有量が０．３５モル％
以上のシリコーン生ゴムを少量添加して、塗布適性を改
善させてもよい。このようにして得られた付加反応型シ
リコーン系樹脂組成物を、該（Ｂ）層の上に塗布し、乾
燥させたのち、通常８０〜１３０℃の温度において３０
〜１２０秒間程度加熱することにより、（Ｃ）層のシリ
コーン系樹脂硬化層が形成される。[0024] Further, this addition reaction type silicone resin composition may have a vinyl group content of 0.35 mol% as desired.
A small amount of the above silicone raw rubber may be added to improve coating suitability. The addition reaction type silicone resin composition obtained in this way is coated on the layer (B), dried, and then heated at a temperature of usually 80 to 130°C for 30 minutes.
By heating for about 120 seconds, a cured silicone resin layer (C) layer is formed.
【００２５】また、紫外線硬化型シリコーン系樹脂組成
物としては、例えば前記一般式［１］で表されるアルケ
ニル基含有オルガノポリシロキサンとメルカプトアルキ
ル基含有オルガノポリシロキサンと増感剤とを含有して
成る組成物などが挙げられる。具体的には主剤としての
東芝シリコーンＵＶ９３００やＵＶ９３０５（東芝シリ
コーン社製、商品名）と硬化触媒としての東芝シリコー
ンＵＶ９３１０Ｃ（東芝シリコーン社製、商品名）との
組合せなどを用いることができる。この紫外線硬化型シ
リコーン系樹脂組成物は、通常有機溶媒を含有する溶液
状で用いられ、このものを該（Ｂ）層に塗布し、乾燥し
て溶媒を除去したのち、紫外線を照射して硬化させるこ
とにより、（Ｃ）層のシリコーン系樹脂硬化層を形成さ
せることができる。Further, the ultraviolet curable silicone resin composition may contain, for example, an alkenyl group-containing organopolysiloxane represented by the general formula [1], a mercaptoalkyl group-containing organopolysiloxane, and a sensitizer. Examples include compositions consisting of: Specifically, a combination of Toshiba Silicone UV9300 or UV9305 (manufactured by Toshiba Silicone Co., Ltd., trade name) as a main ingredient and Toshiba Silicone UV9310C (manufactured by Toshiba Silicone Co., Ltd., trade name) as a curing catalyst can be used. This ultraviolet curable silicone resin composition is usually used in the form of a solution containing an organic solvent, and this is applied to the layer (B), dried to remove the solvent, and then cured by irradiation with ultraviolet rays. By doing so, a cured silicone resin layer of layer (C) can be formed.
【００２６】一方、加熱硬化型シリコーン系樹脂組成物
は、一般に有機溶媒系と水性媒体系とに大別され、前者
の有機溶媒系としては、例えば適当な有機溶媒に前記一
般式［１］で表されるアルケニル基含有オルガノポリシ
ロキサンと、ベンゾイルペルオキシド、２，４−ジクロ
ロベンゾイルペルオキシド、ジクミルペルオキシド、ｐ
−クロロベンゾイルペルオキシドなどの有機過酸化物と
を溶解させて成るもの、あるいはシラン系硬化剤によっ
て硬化するオルガノポリシロキサン、例えばアミノ変性
シリコーンオイルなどとシラン系硬化剤とジブチルスズ
ラウレートなどの触媒とを適当な有機溶媒に溶解して成
るものなどが挙げられる。これらの有機溶媒系加熱硬化
型シリコーン系樹脂組成物を、該（Ｂ）層上に塗布し、
乾燥して溶媒を除去したのち、通常１２０〜２００℃の
範囲の温度において１０分ないし４時間程度加熱硬化さ
せることにより、（Ｃ）層のシリコーン系樹脂硬化層を
形成させることができる。On the other hand, heat-curable silicone resin compositions are generally classified into organic solvent-based and aqueous medium-based. The former organic solvent-based composition includes, for example, a suitable organic solvent with the general formula [1] above. The represented alkenyl group-containing organopolysiloxane, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, dicumyl peroxide, p
- A product obtained by dissolving an organic peroxide such as chlorobenzoyl peroxide, or an organopolysiloxane that is cured by a silane curing agent, such as an amino-modified silicone oil, a silane curing agent, and a catalyst such as dibutyltin laurate. Examples include those obtained by dissolving in a suitable organic solvent. Coating these organic solvent-based heat-curable silicone resin compositions on the layer (B),
After drying to remove the solvent, the cured silicone resin layer of layer (C) can be formed by heating and curing at a temperature generally in the range of 120 to 200° C. for about 10 minutes to 4 hours.
【００２７】また、水性媒体系としては、例えば適当な
水性媒体中に、シラン系硬化剤によって硬化しうるケイ
素化合物、例えばメチルトリメトキシシラン、ヘキシル
トリメトキシシラン、γ−アミノプロピルトリエトキシ
シランなどのアルキルトリアルコキシシランの中から選
ばれた少なくとも１種とシラン系硬化剤とジブチルスズ
ラウレートなどの触媒とを溶解又は懸濁させて成るもの
などが挙げられる。この際用いられる水性媒体としては
、例えば水と低級アルコールとの混合物などが挙げられ
る。In addition, as the aqueous medium system, for example, a silicon compound that can be cured with a silane curing agent, such as methyltrimethoxysilane, hexyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc., is added to a suitable aqueous medium. Examples include those obtained by dissolving or suspending at least one selected from alkyltrialkoxysilanes, a silane curing agent, and a catalyst such as dibutyltin laurate. Examples of the aqueous medium used in this case include a mixture of water and lower alcohol.
【００２８】このようにして得られた水性媒体系加熱硬
化型シリコーン系樹脂組成物を、該（Ｂ）層上に塗布し
、乾燥して溶媒を除去したのち、通常１２０〜２００℃
の範囲の温度において１０ないし４時間程度加熱硬化さ
せることにより、（Ｃ）層のシリコーン系樹脂硬化層を
形成させることができる。また、加熱硬化型シリコーン
系樹脂組成物として、アミノ樹脂によって硬化するオル
ガノポリシロキサンとアミノ樹脂とを含有して成る有機
溶媒系組成物も用いることができる。これらの反応型シ
リコーン系樹脂組成物の中で、特に付加反応型シリコー
ン系樹脂組成物は、比較的低い温度で極めて短時間で硬
化しうるので、生産性がよく好適である。The aqueous medium-based heat-curable silicone resin composition thus obtained is coated on the layer (B), dried to remove the solvent, and then heated at usually 120 to 200°C.
By heating and curing at a temperature in the range of 10 to 4 hours, a cured silicone resin layer of layer (C) can be formed. Furthermore, as the heat-curable silicone resin composition, an organic solvent-based composition containing an amino resin and an organopolysiloxane that is cured by an amino resin can also be used. Among these reactive silicone resin compositions, addition reaction silicone resin compositions are particularly suitable because they can be cured at relatively low temperatures and in an extremely short time, and have good productivity.
【００２９】このようにして形成された（Ｃ）層の反応
型シリコーン系樹脂硬化層の厚さは、通常１〜２０μｍ
の範囲で選ばれる。本発明の離形性シートは、支持基体
の片面に、所望に応じて設けられる（Ａ）層、（Ｂ）層
及び（Ｃ）層を順次設けたものであってもよいし、支持
基体の両面に、前記と同様に各層を設けたものであって
もよい。また、支持基体の片面に各層を設けたものは、
所望に応じ該支持基体の他方の面に感圧接着剤層を、さ
らにその上に場合により剥離シートを設けてもよい。The thickness of the cured reactive silicone resin layer of layer (C) thus formed is usually 1 to 20 μm.
selected within the range. The releasable sheet of the present invention may be one in which layers (A), (B), and (C) are sequentially provided on one side of a support base, as desired, or on one side of a support base. Each layer may be provided on both sides in the same manner as described above. In addition, those in which each layer is provided on one side of the supporting base,
If desired, a pressure-sensitive adhesive layer may be provided on the other surface of the supporting substrate, and a release sheet may be provided thereon.
【００３０】該感圧接着剤層の形成に用いられる感圧接
着剤の基材については特に制限はなく、例えばポリビニ
ルエーテル、ポリイソブチレン、スチレン−ブタジエン
ゴム、ブチルゴム、クロロプレンゴム、塩化ビニル／酢
酸ビニル共重合体、塩化ゴム、ポリビニルブチラールな
ど、従来感圧接着剤に慣用されているものの中から任意
のものを選択して用いてもよい。該感圧接着剤層には、
それを保護する目的で、場合により剥離シートが設けら
れるが、この剥離シートについては特に制限はなく、従
来慣用されているものを用いることができる。There are no particular restrictions on the base material of the pressure-sensitive adhesive used to form the pressure-sensitive adhesive layer, such as polyvinyl ether, polyisobutylene, styrene-butadiene rubber, butyl rubber, chloroprene rubber, vinyl chloride/vinyl acetate. Any adhesive may be selected from those conventionally used in pressure-sensitive adhesives, such as copolymers, chlorinated rubber, and polyvinyl butyral. The pressure sensitive adhesive layer includes:
For the purpose of protecting it, a release sheet is provided in some cases, but there are no particular restrictions on this release sheet, and any conventionally used release sheet can be used.
【００３１】次に、本発明の離形性シートの構成を添付
図面に従って説明すると、図１、図２及び図３は、本発
明の離形性シートのそれぞれ異なった例の構成を示す断
面図であって、図１は、支持基体１の両面に、所望に応
じて設けられる接着剤層（Ａ）２、粉末状無水ケイ酸含
有ウレタン系樹脂又はアクリル系樹脂層（Ｂ）３及び反
応型シリコーン系樹脂硬化層（Ｃ）４が順次に設けられ
た構造を示し、図２は支持基体１の片面のみに、前記と
同様に各層が設けられた構造を示す。また、図３は、支
持基体１の片面に前記と同様に各層が設けられ、かつ支
持基体１の他の面に感圧接着剤層５が、さらに場合によ
り剥離シート６が設けられた構造を示す。Next, the structure of the release sheet of the present invention will be explained with reference to the attached drawings. FIGS. 1, 2, and 3 are cross-sectional views showing the structures of different examples of the release sheet of the present invention. FIG. 1 shows an adhesive layer (A) 2, a powdered silicic anhydride-containing urethane resin or acrylic resin layer (B) 3, and a reactive type adhesive layer (A) 2 provided on both sides of a supporting base 1 as desired. A structure in which cured silicone resin layers (C) 4 are sequentially provided is shown, and FIG. 2 shows a structure in which each layer is provided on only one side of the support base 1 in the same manner as described above. Further, FIG. 3 shows a structure in which each layer is provided on one side of the support base 1 in the same manner as described above, and a pressure-sensitive adhesive layer 5 is provided on the other side of the support base 1, and a release sheet 6 is further provided in some cases. show.
【００３２】本発明の離形性シートは、離形性が良好で
あるとともに、その耐久性にも優れ、繰り返し使用して
も離形性の低下が少なく、粘着性物質取り扱い支持用と
して好適に用いられる。例えば粘着性シートをロール状
に捲層する場合、支持基体の両面に各層が設けられた図
１に示す本発明の離形性シートを、該粘着性シートの粘
着面に重ね、共に捲層することにより、得られたロール
状粘着性シートは、所望の用途に使用する場合、容易に
くり出すことができる。The mold release sheet of the present invention not only has good mold release properties, but also has excellent durability, and even after repeated use, there is little deterioration in mold release properties, making it suitable for use as a support for handling adhesive substances. used. For example, when winding an adhesive sheet into a roll, the release sheet of the present invention shown in FIG. Thereby, the obtained roll-shaped adhesive sheet can be easily rolled out when used for a desired purpose.
【００３３】また、支持基体の片面に各層が設けられた
図２に示す本発明の離形性シートを、粘着性シートの粘
着面に離形性シートの（Ｃ）層４が接するように重ね合
わせることにより、該粘着性シートを保護することがで
きるとともに、粘着性シートの使用時には、離形性シー
トを容易に剥離することができる。さらに、ある基材上
で粘着性物質を取り扱う場合、該基材に粘着性物質が付
着するのを防止するには、図３に示す本発明の離形性シ
ートを用い、場合により設けられた剥離シート６を剥が
し、感圧接着剤層５が該基材面に接するように重ね合わ
せて離形性シートを感圧接着させ、該基材を保護したの
ち、この離形性シート上で粘着性物質を取り扱えばよい
。Further, the release sheet of the present invention shown in FIG. 2, in which each layer is provided on one side of the support substrate, is stacked so that the (C) layer 4 of the release sheet is in contact with the adhesive surface of the adhesive sheet. By combining, the adhesive sheet can be protected, and the release sheet can be easily peeled off when the adhesive sheet is used. Furthermore, when handling an adhesive substance on a certain base material, in order to prevent the adhesive substance from adhering to the base material, the release sheet of the present invention shown in FIG. Peel off the release sheet 6, overlay the release sheet so that the pressure-sensitive adhesive layer 5 is in contact with the surface of the base material, pressure-sensitively adhere the release sheet to protect the base material, and then apply adhesive on the release sheet. You can handle sexual substances.
【００３４】[0034]
【実施例】次に実施例により本発明をさらに詳細に説明
するが、本発明はこれらの例によってなんら限定される
ものではない。
製造例１ ウレタン樹脂系接着剤の製造 セイカボ
ンドＵ−５０７［大日精化工業（株）製、ポリエステル
系ウレタン樹脂接着剤溶液、固形分４５ｗｔ％、粘度約
１５００ｐｓ／２５℃、溶剤トルエン］１００重量部、
架橋剤としてのセイカボンドＵＤ−Ｃ［大日精化工業（
株）製、ポリイソシアネート化合物、固形分７５ｗｔ％
、イソシアネート基含量１２〜１３ｗｔ％、溶剤酢酸エ
チル］８重量部、酢酸エチル５０重量部及び酸化チタン
顔料５重量部を均質に混合して、ウレタン樹脂系接着剤
を製造した。EXAMPLES Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to these examples in any way. Production Example 1 Production of urethane resin adhesive Seikabond U-507 [manufactured by Dainichiseika Kagyo Co., Ltd., polyester urethane resin adhesive solution, solid content 45 wt%, viscosity approximately 1500 ps/25°C, solvent toluene] 100 parts by weight ,
Seikabond UD-C as a crosslinking agent [Dainichiseika Kogyo Co., Ltd.
Co., Ltd., polyisocyanate compound, solid content 75wt%
, isocyanate group content 12 to 13 wt%, solvent ethyl acetate] 8 parts by weight, 50 parts by weight of ethyl acetate, and 5 parts by weight of titanium oxide pigment were homogeneously mixed to produce a urethane resin adhesive.
【００３５】製造例２ アクリル樹脂系接着剤の製造
ブチルアクリレート５モル部と２−ヒドロキシエチ
ルメタクリレート４モル部とメチルメタクリレート１モ
ル部との混合物１００重量部に、ベンゾイルペルオキシ
ド２重量部を加え、公知の方法により酢酸エチル中で共
重合させ、固形分含有量４０ｗｔ％、粘度５２００ｃｐ
ｓ／２５℃のアクリル樹脂溶液を製造した。次に、この
アクリル樹脂溶液１００重量部、セイカボンドＵＤ−Ｃ
［大日精化工業（株）製、イソシアネート系硬化剤］５
重量部及び酢酸エチル２０重量部を混合して、アクリル
樹脂系接着剤を製造した。Production Example 2 Production of acrylic resin adhesive 2 parts by weight of benzoyl peroxide was added to 100 parts by weight of a mixture of 5 mol parts of butyl acrylate, 4 mol parts of 2-hydroxyethyl methacrylate and 1 mol part of methyl methacrylate. Copolymerized in ethyl acetate by the method of
An acrylic resin solution was prepared at s/25°C. Next, 100 parts by weight of this acrylic resin solution, Seikabond UD-C
[Isocyanate curing agent manufactured by Dainichiseika Kogyo Co., Ltd.] 5
Parts by weight and 20 parts by weight of ethyl acetate were mixed to produce an acrylic resin adhesive.
【００３６】製造例３ ウレタン系樹脂溶液の（イ）
の製造
１，４−ブタンジオールアジペートポリオール（水
酸基価約５６、分子量約２０００、２官能性ポリオール
）２０００ｇ、１，４−ブタンジオール４５ｇ、ＭＤＩ
（ジフェニルメタンジイソシアネート）３２０ｇ、ジメ
チルホルムアミド１００ｇ及びメチルエチルケトン１０
０ｇを１０リットルの反応器に仕込み、常温（約２５℃
）から約９５℃まで１時間を要して昇温し、この温度で
２時間反応させたのち、これにジブチルスズラウレート
０．１ｇ、ＭＤＩ５５ｇ、ジメチルホルムアミド７８２
ｇ及びメチルエチルケトン３６４ｇを加え、さらに約９
５℃で２時間反応させ、次いで放冷却しながらジメチル
ホルムアミド１０００ｇ及びメチルエチルケトン３００
０ｇを添加し、ウレタン系樹脂溶液（イ）を製造した。
このウレタン系樹脂溶液（イ）の粘度は約３００ｐｓ／
２５℃、固形分含有量は約３０ｗｔ％であり、また、赤
外分析の結果、イソシアネート基に起因するピークはほ
とんど検出されなかった。なお、反応に用いた原料のＮ
ＣＯ／ＯＨモル比は約１．０であった。Production Example 3 Urethane resin solution (a)
Production of 1,4-butanediol adipate polyol (hydroxyl value approximately 56, molecular weight approximately 2000, bifunctional polyol) 2000 g, 1,4-butanediol 45 g, MDI
(diphenylmethane diisocyanate) 320g, dimethylformamide 100g and methyl ethyl ketone 10
Pour 0g into a 10 liter reactor and keep it at room temperature (approximately 25℃).
) to about 95°C over 1 hour, and after reacting at this temperature for 2 hours, 0.1 g of dibutyltin laurate, 55 g of MDI, and 782 g of dimethylformamide were added to this.
g and 364 g of methyl ethyl ketone, and further approximately 9 g.
The reaction was carried out at 5°C for 2 hours, and then 1000 g of dimethylformamide and 300 g of methyl ethyl ketone were added while cooling.
0 g was added to produce a urethane resin solution (a). The viscosity of this urethane resin solution (a) is approximately 300 ps/
At 25° C., the solid content was about 30 wt%, and as a result of infrared analysis, almost no peaks due to isocyanate groups were detected. In addition, the raw material N used for the reaction
The CO/OH molar ratio was approximately 1.0.
【００３７】製造例４ ウレタン系樹脂溶液（ロ）の
製造
１，４−ブタンジオールアジペートポリオール（水
酸基価約５６、分子量約２０００、２官能性ポリオール
）２０００ｇ、イソホロンジイソシアネート４４４ｇ（
ＮＣＯ／ＯＨモル比約２）及びメチルエチルケトン８１
５ｇを１０リットルの反応器に仕込み、常温（約２５℃
）から約９５℃まで１時間を要して昇温したのち、この
温度で４時間反応させて末端イソシアネート基含有ウレ
タンプレポリマー溶液（固形分７５ｗｔ％）を得た。こ
れに、さらにメチルエチルケトン１６２９ｇを添加して
固形分含有量５０ｗｔ％のウレタンプレポリマー溶液を
調製した。この溶液中のイソシアネート基の含有量は１
．７１８ｗｔ％であった。次に、５リットルの反応器に
イソプロピルアルコール４１６ｇ、メチルエチルケトン
３３４ｇ、イソホロンジアミン３３．０３ｇ（鎖伸長率
９５％）及びＤＢＡ（重合禁止剤添加率５％）２．６４
ｇを仕込み、約３０℃に調温しながら、さらに前記の固
形分５０ｗｔ％のウレタンプレポリマー溶液１０００ｇ
を添加して激しく撹拌した。次いで、撹拌しながら、１
時間を要して約４０℃まで昇温し、さらにこの温度で２
時間反応させたのち、放冷却してウレタン系樹脂溶液（
ロ）を製造した。このウレタン系樹脂溶液（ロ）の固形
分含有量は３０ｗｔ％で、粘度は２００ｐｓ／２５℃で
あった。Production Example 4 Production of urethane resin solution (b) 2000 g of 1,4-butanediol adipate polyol (hydroxyl value about 56, molecular weight about 2000, bifunctional polyol), 444 g of isophorone diisocyanate (
NCO/OH molar ratio approximately 2) and methyl ethyl ketone 81
Pour 5g into a 10 liter reactor and heat at room temperature (approximately 25°C).
) to about 95° C. over a period of 1 hour, and then reacted at this temperature for 4 hours to obtain a urethane prepolymer solution (solid content: 75 wt %) containing terminal isocyanate groups. To this, 1629 g of methyl ethyl ketone was further added to prepare a urethane prepolymer solution having a solid content of 50 wt%. The content of isocyanate groups in this solution is 1
．． It was 718 wt%. Next, in a 5 liter reactor, 416 g of isopropyl alcohol, 334 g of methyl ethyl ketone, 33.03 g of isophorone diamine (chain extension rate 95%) and 2.64 g of DBA (polymerization inhibitor addition rate 5%) were added.
g, and while controlling the temperature to about 30°C, add 1000 g of the above-mentioned urethane prepolymer solution with a solid content of 50 wt%.
was added and stirred vigorously. Then, while stirring, 1
It takes time to raise the temperature to about 40℃, and at this temperature
After reacting for a period of time, the urethane resin solution (
b) was manufactured. The solid content of this urethane resin solution (b) was 30 wt%, and the viscosity was 200 ps/25°C.
【００３８】製造例５ 付加反応型シリコーン系樹脂
溶液（イ）の製造
メチルフェニルシロキサン単位７０モル％、メチル
ビニルシロキサン単位１０モル％及びジメチルシロキサ
ン単位２０モル％から成り、かつ両末端にメチル基とフ
ェニル基とビニル基とを含有するオルガノポリシロキサ
ン（粘度２１００ｃｐｓ／２５℃）９０重量部、粘度調
節剤としてのオルガノポリシロキサン１０重量部、テト
ラメチルテトラハイドロジエンシロキサン１５重量部、
白金とテトラメチルジビニルジシロキサン錯体１重量部
（白金含有量０．６重量％）、重合禁止剤としてのｎ−
ブタノール１重量部及びトルエン５００重量部から成る
付加反応型シリコーン系樹脂溶液（イ）を製造した。Production Example 5 Production of addition reaction type silicone resin solution (a) Consists of 70 mol% of methylphenylsiloxane units, 10 mol% of methylvinylsiloxane units and 20 mol% of dimethylsiloxane units, and has methyl groups at both ends. 90 parts by weight of organopolysiloxane containing phenyl groups and vinyl groups (viscosity 2100 cps/25°C), 10 parts by weight of organopolysiloxane as a viscosity modifier, 15 parts by weight of tetramethyltetrahydrodienesiloxane,
1 part by weight of platinum and tetramethyldivinyldisiloxane complex (platinum content 0.6% by weight), n- as a polymerization inhibitor
An addition reaction type silicone resin solution (a) consisting of 1 part by weight of butanol and 500 parts by weight toluene was produced.
【００３９】製造例６ 付加反応型シリコーン系樹脂
溶液（ロ）の製造
両末端にメチル基、フェニル基及びビニル基を有す
るジメチルポリシロキサン（粘度１９００ｃｐｓ／２５
℃）９５重量部、両末端ハイドロジエンジメチルポリシ
ロキサン（粘度２０ｃｐｓ／２５℃）５重量部、両末端
にトリメチルシリル基含有メチルハイドロジエンシロキ
サン共重合体（粘度２０ｃｐｓ／２５℃）１重量部、粘
度調節剤としてＴＳＥ３２２１［東芝シリコーン（株）
製、ミラブルシリコーンゴム］５重量部、白金とテトラ
メチルジビニルジシロキサン錯体１．２重量部（白金含
有量０．６重量％）、重合禁止剤としてのｎ−ブタノー
ル１重量部及びトルエン５００重量部から成る付加反応
型シリコーン系樹脂溶液（ロ）を製造した。Production Example 6 Production of addition reaction type silicone resin solution (b) Dimethylpolysiloxane having methyl groups, phenyl groups and vinyl groups at both ends (viscosity 1900 cps/25
°C) 95 parts by weight, 5 parts by weight of hydrodiene dimethyl polysiloxane at both ends (viscosity 20 cps/25 °C), 1 part by weight of methylhydrogen siloxane copolymer containing trimethylsilyl groups at both ends (viscosity 20 cps/25 °C), viscosity adjustment As an agent, TSE3221 [Toshiba Silicone Corporation]
5 parts by weight of platinum and tetramethyldivinyldisiloxane complex (platinum content: 0.6% by weight), 1 part by weight of n-butanol as a polymerization inhibitor, and 500 parts by weight of toluene. An addition reaction type silicone resin solution (b) consisting of the following was produced.
【００４０】実施例１〜８、比較例１〜８第１表に示す
組成の（Ｂ）層形成用ウレタン系樹脂組成物、第２表に
示す組成の（Ｃ）層形成用反応型シリコーン系樹脂組成
物を調製した。なお、反応型シリコーン系樹脂組成物を
調製する場合、あらかじめ白金系触媒以外の成分を均質
に溶解又は分散させておいてから、これに白金系触媒を
添加した。Examples 1 to 8, Comparative Examples 1 to 8 (B) Urethane resin composition for layer formation having the composition shown in Table 1, (C) Reactive silicone resin composition for layer formation having the composition shown in Table 2 A resin composition was prepared. When preparing the reactive silicone resin composition, the components other than the platinum catalyst were homogeneously dissolved or dispersed in advance, and then the platinum catalyst was added thereto.
【００４１】[0041]
【表１】[Table 1]
【００４２】注
１）セイカボンドＵＤ−Ｃ（硬化剤）
大日精化工業（株）製、トリレンジイソシアネート付加
体、固形分７５ｗｔ％、ＮＣＯ含量１２〜１３ｗｔ％、
溶剤酢酸エチル
２）無水ケイ酸
富士デビソン社製、サイロイド＃２４４[0042] Note 1) Seikabond UD-C (curing agent) manufactured by Dainichiseika Kagyo Co., Ltd., tolylene diisocyanate adduct, solid content 75 wt%, NCO content 12 to 13 wt%,
Solvent ethyl acetate 2) Anhydrous silicic acid manufactured by Fuji Davison, Cyroid #244
【００４３】[0043]
【表２】[Table 2]
【００４４】注
１）無水ケイ酸
富士デビソン社製、サイロイド＃２４４まず、離形紙に
第３表に示すウレタン系樹脂組成物を１００ｇ／ｍ２の
割合で塗布したのち、１００℃で６０秒間熱風乾燥して
乾燥皮膜を形成後、ただちに、この上に製造例１で得ら
れたウレタン樹脂系接着剤を１００ｇ／ｍ２の割合で塗
布し、同様にして乾燥皮膜を形成させながら、ナイロン
繊維の平織り織布と貼り合わせ巻き取り、さらに２５〜
３０℃で約１２時間熟成した。次いで、離形紙を剥離し
たのち、ウレタン系樹脂層の上に第３表に示す種類の反
応型シリコーン系樹脂組成物をグラビアロールコーター
で３０ｇ／ｍ２の割合で塗布し、１００℃で６０秒間熱
風乾燥させてシリコーン系樹脂硬化層を形成させ、離形
性シートを作成した。Note 1) Anhydrous silicic acid manufactured by Fuji Davison Co., Ltd., Thyroid #244 First, the urethane resin composition shown in Table 3 was applied to release paper at a rate of 100 g/m2, and then heated with hot air at 100°C for 60 seconds. Immediately after drying to form a dry film, the urethane resin adhesive obtained in Production Example 1 was applied thereon at a rate of 100 g/m2, and while forming a dry film in the same manner, a plain weave of nylon fiber was applied. Paste and wind the woven fabric, then continue for 25~
It was aged at 30°C for about 12 hours. Next, after peeling off the release paper, a reactive silicone resin composition of the type shown in Table 3 was applied onto the urethane resin layer at a rate of 30 g/m2 using a gravure roll coater, and then heated at 100°C for 60 seconds. A cured silicone resin layer was formed by drying with hot air, and a releasable sheet was prepared.
【００４５】このようにして得られた離形性シートにつ
いて、表面のシリコーン系樹脂硬化層の接着強度と反応
型シリコーン系樹脂組成物の調製直後から塗布硬化する
までの経過時間との関係を求めた。なお、反応型シリコ
ーン系樹脂組成物の調製直後とは、反応型シリコーン系
樹脂溶液を含む組成物に白金系触媒を添加した時点をい
う。また、接着強度はＪＩＳ Ｌ−０８２３、Ｌ−０８
４９に準拠して求めた。ただし、摩擦試験部分に取り付
ける金巾４号の代わりに、ＰＬＡＳＴＩＣＥＲＡＳＥＲ
ケシ−１（コクヨ製）を取り付け、加重１ｋｇで摩擦試
験を行い、該シリコーン系樹脂硬化層が脱落するまでの
摩擦回数を接着強度の指標として求めた。その結果を第
３表に示す。Regarding the release sheet thus obtained, the relationship between the adhesive strength of the cured silicone resin layer on the surface and the elapsed time from immediately after the preparation of the reactive silicone resin composition until the application and curing was determined. Ta. Note that "immediately after preparing the reactive silicone resin composition" refers to the time when the platinum catalyst is added to the composition containing the reactive silicone resin solution. In addition, the adhesive strength is JIS L-0823, L-08.
49. However, instead of the gold width No. 4 attached to the friction test part, PLASTICERASER
Keshi-1 (manufactured by KOKUYO) was attached and a friction test was conducted under a load of 1 kg, and the number of times of friction until the cured silicone resin layer fell off was determined as an index of adhesive strength. The results are shown in Table 3.
【００４６】[0046]
【表３】[Table 3]
【００４７】[0047]
【表４】[Table 4]
【００４８】第３表から分かるように、本発明の離形性
シートは、比較例のものに比べ、シリコーン系樹脂硬化
層の接着性に優れ、かつ反応型シリコーン系樹脂組成物
を調製してから、塗布硬化させるまで、常温で４時間経
過しても、シリコーン系樹脂硬化層の接着強度はほとん
ど低下しない。また、アクリル樹脂系粘着剤層が設けら
れたポリエチレンフイルム及びＳＢＲ系粘着剤層が設け
られた綿織布を用意し、それぞれの粘着剤層の上に、実
施例１〜８及び比較例１〜８の離形性シートを、シリコ
ーン系樹脂硬化層が接するように密着させて、その剥離
抵抗を観察したところ、いずれも剥離に必要な抵抗はほ
とんど感じられなかった。As can be seen from Table 3, the release sheet of the present invention has superior adhesion of the cured silicone resin layer compared to the comparative example, and is superior in adhesiveness to the cured silicone resin layer, and is superior to those of the comparative example. The adhesive strength of the cured silicone resin layer hardly decreases even after 4 hours have passed at room temperature from the time of application to the time of curing. In addition, a polyethylene film provided with an acrylic resin adhesive layer and a cotton woven fabric provided with an SBR adhesive layer were prepared, and Examples 1 to 8 and Comparative Examples 1 to 8 were coated on each adhesive layer. When the release sheet No. 8 was brought into close contact with the cured silicone resin layer and its peel resistance was observed, almost no resistance necessary for peeling was felt in any case.
【００４９】実施例９
アクリル樹脂層をベースとする離形性シートを下記の方
法で製造した。
ａ）アクリル樹脂接着剤溶液配合（Ａ層）製造例２に示
したアクリル樹脂溶液（固形分４０％、粘度５２００ｃ
ｐｓ）
ｂ）無水ケイ酸含有アクリル樹脂層（Ｂ層）製造例２に
示したアクリル樹脂溶液（固形分４０％、粘度５２００
ｃｐｓ）
ｃ）離形性シートの製造
離形紙に、上記ａ）に示したアクリル樹脂接着剤配合組
成物を約１００ｇ／ｍ２・ｗｅｔ塗布乾燥（約９０〜１
００℃／２〜３分間）しながらナイロン平織布とラミネ
ートし巻き取り、常温で１２時間熟成した（以下これを
原反ＡＡという）。続いて、離形紙に、上記ｂ）に示し
た無水ケイ酸含有アクリル樹脂配合組成物を約１００ｇ
／ｍ２・ｗｅｔ塗布乾燥しながら（約９０〜１００℃／
２〜３分間）、一方同時に原反ＡＡから離形紙を剥離し
ながら、これらをラミネートし温度約３０〜４０℃で１
２時間熟成した（以下これを原反ＢＢという）。このよ
うにして得られた原反ＢＢに対して実施例１と同様にし
て、表３に示す種類の反応型シリコン系樹脂組成物をグ
ラビヤロールコーターで約３０ｇ／ｍ２の割合で塗布し
、１００℃で６０秒間乾燥させてシリコン系樹脂硬化層
を形成させ離形性シートを得た。Example 9 A releasable sheet based on an acrylic resin layer was produced by the following method. a) Acrylic resin adhesive solution formulation (A layer) Acrylic resin solution shown in Production Example 2 (solid content 40%, viscosity 5200c)
ps) b) Silicic anhydride-containing acrylic resin layer (B layer) Acrylic resin solution shown in Production Example 2 (solid content 40%, viscosity 5200
cps) c) Manufacture of release sheet Apply approximately 100 g/m2 of the acrylic resin adhesive compounded composition shown in a) above to release paper and dry (approximately 90 to 1
00°C for 2 to 3 minutes), the film was laminated with a nylon plain woven fabric, wound up, and aged at room temperature for 12 hours (hereinafter referred to as original fabric AA). Next, about 100 g of the silicic anhydride-containing acrylic resin composition shown in b) above was placed on the release paper.
/m2・Wet coating while drying (approximately 90-100℃/
2 to 3 minutes), while simultaneously peeling off the release paper from the original fabric AA, laminate them and heat at a temperature of about 30 to 40°C.
It was aged for 2 hours (hereinafter referred to as the original fabric BB). In the same manner as in Example 1, the raw fabric BB thus obtained was coated with a reactive silicone resin composition of the type shown in Table 3 at a rate of about 30 g/m2 using a gravure roll coater. It was dried at .degree. C. for 60 seconds to form a cured silicone resin layer to obtain a releasable sheet.
【００５０】実施例１０
実施例１と同様にして、ナイロン織布の両面に、ウレタ
ン樹脂系接着剤層、無水ケイ酸含有ウレタン系樹脂層及
びシリコーン系樹脂硬化層を形成させ、離形性シートを
作製した。Example 10 In the same manner as in Example 1, a urethane resin adhesive layer, a silicic anhydride-containing urethane resin layer, and a cured silicone resin layer were formed on both sides of a nylon woven fabric to form a release sheet. was created.
【００５１】実施例１１
実施例１と同様にして、ナイロン織布の片面にウレタン
樹脂系接着剤層、無水ケイ酸含有ウレタン系樹脂層及び
シリコーン系樹脂硬化層を形成させたのち、該ナイロン
織布の裏面にＳＢＲ系感圧接着剤層を設け、さらにその
上に剥離紙を貼付し、離形性シートを作製した。Example 11 In the same manner as in Example 1, a urethane resin adhesive layer, a silicic anhydride-containing urethane resin layer, and a silicone resin hardening layer were formed on one side of a nylon woven fabric. An SBR pressure-sensitive adhesive layer was provided on the back side of the cloth, and a release paper was attached thereon to produce a release sheet.
【００５２】[0052]
【発明の効果】本発明の離形性シートは離形性及びその
耐久性に優れる上、簡単な工程で容易に生産性よく製造
することができ、粘着性物質を取り扱う際の支持用とし
て好適に用いられる。[Effects of the Invention] The release sheet of the present invention has excellent release properties and durability, and can be manufactured easily and with high productivity through a simple process, making it suitable for use as a support when handling adhesive substances. used for.
【００５３】[0053]
【図１】本発明の離形性シートの１例の構成を示す断面
図である。FIG. 1 is a sectional view showing the structure of an example of a release sheet of the present invention.
【００５４】[0054]
【図２】本発明の離形性シートの異なった例の構成を示
す断面図である。FIG. 2 is a sectional view showing the configuration of different examples of the release sheet of the present invention.
【００５５】[0055]
【図３】本発明の離形性シートの別の異なった例の構成
を示す断面図である。FIG. 3 is a sectional view showing the structure of another different example of the release sheet of the present invention.
【００５６】[0056]
１ 支持基体
２ 必要に応じ設けられる接着剤層
３ 無水ケイ酸含有ウレタン系樹脂又はアクリレート
系樹脂層
４ 反応型シリコーン系樹脂硬化層
５ 感圧接着剤層1 Support base 2 Adhesive layer provided as necessary 3 Silicic anhydride-containing urethane resin or acrylate resin layer 4 Reactive silicone resin cured layer 5 Pressure-sensitive adhesive layer
Claims (3)
設けられる（Ａ）接着剤層、（Ｂ）粉末状無水ケイ酸含
有ウレタン系樹脂又はアクリル系樹脂層及び（Ｃ）反応
型シリコーン系樹脂硬化層を順次設けて成る離形性シー
ト。[Claim 1] (A) an adhesive layer, (B) a powdered silicic anhydride-containing urethane resin or acrylic resin layer, and (C) a reactive silicone layer, which are provided on one or both sides of a supporting base as desired. A releasable sheet made of sequential resin cured layers.
る（Ａ）接着剤層、（Ｂ）粉末状無水ケイ酸含有ウレタ
ン系樹脂又はアクリル系樹脂層及び（Ｃ）反応型シリコ
ーン系樹脂硬化層を順次設け、かつ該支持基体の他方の
面に、感圧接着剤層を、さらに場合により剥離用シート
を設けて成る離形性シート。2. (A) an adhesive layer, (B) a powdered silicic anhydride-containing urethane resin or acrylic resin layer, and (C) a reactive silicone resin, provided on one side of the supporting base as desired. A releasable sheet comprising cured layers successively provided, a pressure sensitive adhesive layer, and optionally a release sheet provided on the other surface of the support base.
系樹脂１００重量部に対し、粉末状無水ケイ酸１〜５０
重量部を含有させたものから成る請求項１又は２記載の
離形性シート。3. The layer (B) contains 1 to 50 parts of powdered silicic anhydride to 100 parts by weight of the urethane resin or acrylic resin.
The releasable sheet according to claim 1 or 2, comprising a part by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16644291A JPH0730293B2 (en) | 1991-06-11 | 1991-06-11 | Release sheet |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16644291A JPH0730293B2 (en) | 1991-06-11 | 1991-06-11 | Release sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04363377A true JPH04363377A (en) | 1992-12-16 |
| JPH0730293B2 JPH0730293B2 (en) | 1995-04-05 |
Family
ID=15831483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16644291A Expired - Fee Related JPH0730293B2 (en) | 1991-06-11 | 1991-06-11 | Release sheet |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730293B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0611645A2 (en) * | 1993-02-18 | 1994-08-24 | AMOENA Medizin-Orthopädie-Technik GmbH | Connection element |
| US5538780A (en) * | 1993-02-18 | 1996-07-23 | Amoena Medizin-Orthop adietechnik GmbH | Connecting element using silicic acid particles to provide detachable adhesion |
| JP2006087462A (en) * | 2004-09-21 | 2006-04-06 | Zenjiro Shiozu | Bonding structure between skin side and ball side of ball for ball game |
| JP2006289801A (en) * | 2005-04-11 | 2006-10-26 | Lintec Corp | Release sheet and self-adhering body |
| JP2012245746A (en) * | 2011-05-30 | 2012-12-13 | Iwao Kk | Mold-release sheet member |
-
1991
- 1991-06-11 JP JP16644291A patent/JPH0730293B2/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0611645A2 (en) * | 1993-02-18 | 1994-08-24 | AMOENA Medizin-Orthopädie-Technik GmbH | Connection element |
| EP0611645A3 (en) * | 1993-02-18 | 1995-07-26 | Amoena Med Orthopaedie Tech | Connection element. |
| US5538780A (en) * | 1993-02-18 | 1996-07-23 | Amoena Medizin-Orthop adietechnik GmbH | Connecting element using silicic acid particles to provide detachable adhesion |
| JP2006087462A (en) * | 2004-09-21 | 2006-04-06 | Zenjiro Shiozu | Bonding structure between skin side and ball side of ball for ball game |
| JP4656898B2 (en) * | 2004-09-21 | 2011-03-23 | 善治郎 潮津 | Adhesion method between outer skin side and ball side in ball game balls |
| JP2006289801A (en) * | 2005-04-11 | 2006-10-26 | Lintec Corp | Release sheet and self-adhering body |
| JP2012245746A (en) * | 2011-05-30 | 2012-12-13 | Iwao Kk | Mold-release sheet member |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0730293B2 (en) | 1995-04-05 |
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